Hydrogen permeation properties of CrxCy@Cr2O3/Al2O3 composite coating derived from selective oxidation of a CrC alloy and atomic layer deposition

Metal oxides and carbides are promising tritium permeation barrier coatings for fusion reactors. However, the thermomechanical mismatch between the coating and substrate poses a threat to their interface's integrity during fabrication and operation. To address this issue, a metallic interlayer coating was introduced followed by selective oxidation in which a compact and uniform CrC amorphous alloy coating was successfully deposited on the stainless steel substrate by pulsed electrochemical deposition. A new composite coating of Cr_xC_y@Cr₂O₃/Al₂O₃ was formed by subsequent controlled oxidation conversion and atomic layer deposition. The phase, morphology, chemical state and defects of the films were analyzed and compared both before and after hydrogen exposure at 300 °C. The results show that this new kind of composite coating, based on the principles of grain boundary pinning of chromic oxide with carbide and defect healing of alumina, can remarkably improve the hydrogen permeation barrier performance of these materials.     

Hydrogen interaction characteristics of a Cr2O3Y2O3 coating formed on stainless steel in an ultra-low oxygen environment

Ceramics are the most promising candidates for tritium permeation barriers for fusion reactors due to their high thermal and chemical stabilities and low hydrogen isotope permeation reduction factors. However, hydrogen embrittlement and a large number of defects in ceramic coatings are new challenges for first wall materials in nuclear reactors. To address this issue, a new Cr₂O₃Y₂O₃ coating with a thickness of about 100 nm was synthesized and placed in an ultra-low oxygen partial pressure (8 × 10⁻²⁰ Pa) environment, in which a compact CrY alloy coating was successfully deposited on the stainless-steel substrate by pulsed electrochemical deposition. The interactions between the coating and hydrogen plasma were comprehensively analyzed and compared via surface analysis techniques, including TEM, XPS and electrochemical impedance spectroscopy (EIS). The mechanical properties of the coating before and after hydrogen permeation were studied by tensile testing. It was found that this ceramic coating effectively reduced the defect concentration and retained a high protective performance upon hydrogen exposure. Therefore, this new Cr₂O₃Y₂O₃ coating has potential as a promising hydrogen permeation barrier.     

Hydrogen interaction characteristic of nanoscale oxide films grown on iron–nickel based stainless steel by selective thermal oxidation

Hydrogen isotopes, the reaction ingredients in the nuclear fusion plant, can easily permeate through the stainless steel (SS) substrate, leading to the so-called hydrogen degradation. Generally, a widely accepted way to reduce the hydrogen permeation is to prepare a barrier coating on the substrate. Nevertheless, the coated layer has the inherent problem of incompatibility with the heterogeneous base materials. In this work, in-situ selective oxidation was used to explore the optimal oxides with the improved hydrogen resistance. Two types of layers thermally formed at 450 °C and 750 °C, respectively, were selected to investigate their hydrogen interaction characteristics. Comprehensive analyses, including Raman spectra, XPS, EIS and AES, indicate that the oxide formed at 450 °C is a better candidate of hydrogen permeation barriers, probably due to the formation of protective layers of chromia and FeCr₂O₄, while the oxides obtained at 750 °C, though exhibiting a much more stable phase, can rarely reduce hydrogen diffusion through the shortcuts of defects. This finding provides a potential new way to prepare a hydrogen permeation barrier.     

Preparation of Cr2O3/Al2O3 bipolar oxides as hydrogen permeation barriers by selective oxide removal on SS and atomic layer deposition

Iron-nickel based stainless steel (SS) applied in nuclear plants as a substrate material barely suppresses the permeation of hydrogen plasmas, which are mainly composed of positive and negative hydrogen ions with trace amounts of non-ionized hydrogen atoms. In this work, a new Cr₂O₃/Al₂O₃ bipolar oxide barrier was prepared using atomic layer deposition (ALD) of Al₂O₃ on a Cr₂O₃ layer that was generated by removing partial oxides with cyclic voltammetry (CV) of SS that had been pre-oxidized at 550 °C in air. We found that a small layer of α-Al₂O₃ was formed by the template effect of Cr₂O₃ at the interface of this composite film. The hydrogen permeation behavior of this bipolar oxide barrier in a fusion reactor was simulated with hydrogen-discharging plasma treatment. The results demonstrated that the hydrogen permeation resistance of this bipolar oxide was superior to the original oxide or a Cr₂O₃ film. Impressively, hydrogen plasma treatment repaired the bipolar oxide via reduction of the defective CrO₃, resulting in an improvement in the hydrogen permeation resistance. These findings demonstrate a novel method of hydrogen permeation barrier preparation on SS, providing insight into hydrogen barrier construction for future nuclear energy applications.     

MoS2/Mo2TiC2Tx supported Pd nanoparticles as an efficient electrocatalyst for hydrogen evolution reaction in both acidic and alkaline media

Development of electrocatalytic hydrogen production technology is the key to solving environmental and energy problems. Two-dimensional material Mo₂TiC₂T_x (T_x = –OH, –F) has shown great potential in electrocatalytic hydrogen evolution because of its excellent conductivity and hydrophilicity. However, due to the lack of sufficient active sites of Mo₂TiC₂T_x itself, its practical applications in electrocatalytic hydrogen evolution are limited. In this work, a highly-efficient hydrogen evolution electrocatalyst, namely Pd@MoS₂/Mo₂TiC₂T_x, is prepared through a simple pyrolysis method. In such a composite, the MoS₂ nanoflowers hybridized with the ammonia-treated Mo₂TiC₂T_x (MoS₂/Mo₂TiC₂T_x) are used as a substrate for loading a small number of Pd nanoparticles (4.27 at.%). Notably, the introduction of Pd nanoparticles into MoS₂/Mo₂TiC₂T_x provides abundant active sites for the hydrogen evolution reaction, improves the conductivity of the electrocatalyst, speeds up the adsorption and desorption of hydrogen, and induces a synergistic effect with the MoS₂. As a result, the Pd@MoS₂/Mo₂TiC₂T_x catalyst exhibits excellent electrocatalytic performance and remarkable stability in both acidic and alkaline media. In a 0.5 mol/L H₂SO₄ electrolyte, the overpotential of Pd@MoS₂/Mo₂TiC₂T_x was 92 mV with a Tafel slope of 60 mV/dec at a current density of 10 mA/cm². Meanwhile, the catalyst displayed an overpotential of 100 mV associated with a Tafel slope of 80 mV/dec at the current density of 10 mA/cm² in a 1 mol/L KOH electrolyte. This work shows the great potential of using Mo₂TiC₂T_x-based material in the field of electrocatalysis.     

The influence of stacking faults on hydrogen storage in TiCx

The hydrogen storage ability of TiC_x with stacking faults (SFs) is studied in this work. It is found that the absorption of hydrogen atoms is possible in both TiC_x with and without SFs. And, besides the carbon vacancy sites, the hydrogen atoms can also occupy the tetrahedral sites in the SFs layers. More importantly, it is confirmed that the diffusion of hydrogen in TiC_x with SFs is much easier than that in TiC_x without SFs, especially the diffusion around the SFs layers. The energy barrier for diffusion of the hydrogen atom in the SFs layers and diffusion from the SF layer to the next layer is only 0.099 eV and 0.185 eV, respectively. Therefore, bringing in the SFs in TiC_x with ordered carbon vacancies will be an effective method to solve the diffusion problem during the processes of hydrogen storage.     

Graphite coating on alumina substrate for the fabrication of hydrogen selective membranes

Development of composite membranes is a suitable alternative to improve the hydrogen flux through palladium membranes. The porous substrate should not represent a barrier to gas permeation, but the roughness of its surface should be sufficiently smooth for the deposition of a thin and defect-free metal layer. In this study, the performances of the modification of the outer surface of an asymmetric alumina hollow fibre substrate by the deposition of a graphite layer were evaluated. The roughness of the substrate outer surface was reduced from 120 to 37 nm after graphite coating. After graphite coating, the hydrogen permeance through the composite membrane produced with 2 Pd plating cycles was of 1.02 × 10^?3 mol s^?1 m^?2 kPa^?1 at 450 °C and with infinite H₂/N₂ selectivity. Similar hydrogen permeance was obtained with the composite membrane without graphite coating, also at infinite H₂/N₂ selectivity, but 3 Pd plating cycles were necessary. Thus, graphite coating on asymmetric alumina hollow fibres is a suitable alternative to reduce the required palladium amount to produce hydrogen selective membranes.     

Application of a deep eutectic solvent to prepare nanocrystalline Ni and Ni/TiO2 coatings as electrocatalysts for the hydrogen evolution reaction

The paper reports the electrochemical deposition of nanocrystalline nickel and composite nickel-titania films as effective electrocatalysts for the hydrogen evolution reaction. To produce the composite Ni/TiO₂ electrodeposits, a plating bath based on a deep eutectic solvent, a novel kind of ionic liquids, was used for the first time. The electrolyte contained ethaline (a eutectic mixture of choline chloride and ethylene glycol), 1 M NiCl₂⋅6H₂O and the addition of extra water (3, 6, 9 mol dm⁻³). Titania dispersed phase was introduced into the electrolyte as nanopowder Degussa P 25 (0–10 g dm⁻³). It was shown that the introduction of extra water to the plating bath allowed appreciably increasing the content of TiO₂ phase in the coating (from ca. 2 to 10 wt%). The effects of electrolysis conditions on the TiO₂ content in the coatings, surface morphology and microstructure were determined. The results of voltammetry measurements showed that the Ni and composite Ni/TiO₂ coatings electrodeposited from the plating electrolyte based on a deep eutectic solvent exhibit improved electrocatalytic properties towards the hydrogen evolution reaction as compared with deposits obtained from commonly used aqueous electrolytes. The mechanism of the hydrogen evolution reaction on the Ni and composite Ni/TiO₂ coatings is a combination of Volmer-Heyrovsky reactions. The introduction of TiO₂ particles into the nickel matrix results in the acceleration of the hydrogen evolution reaction. An improved catalytic activity of Ni/TiO₂ composites towards the hydrogen evolution reaction can be associated with the presence of titanium-containing redox couples on the surface.     

Multiphase Nb–TiCo alloys: The significant impact of surface corrosion on the structural stability and hydrogen permeation behaviour

Multiphase Nb_xTi_(100-x)/2Co_(100-x)/2 (x = 30–60) alloys are a promising material for hydrogen separating membranes. These alloy membranes exhibit a rapid decline in hydrogen permeation flux within ∼12 h when operated at 773 K. To address this issue, a dense oxide (e.g. Nb₂O₅, TiO₂ and CoO) layer was prepared between a Pd coating layer and an Nb–TiCo substrate by surface corrosion for improving their thermal stability, and the corrosion resistance of Nb–TiCo alloys was investigated. An increase in the Nb content (x) lowers the corrosion resistance of these alloys, but makes it easier to form the above oxide layer. Substantial enhancement of hydrogen permeability and thermal stability at 773 K was observed for the alloys (x = 30 and 40) after corrosion, which can be ascribed to an increase in hydrogen diffusivity. This improved permeability and stability are closely related to the formation of the above surface oxide layer that impeded interdiffusion between the Pd film and Nb–TiCo substrates. This study demonstrates that insertion of a diffusion barrier between the Pd and Nb-based substrates by surface corrosion is a viable approach to enhance the high-temperature stability of Pd-coated Nb–TiCo alloys, an aspect not widely explored in Nb-based hydrogen separation and purification membranes.     

High performance hydrogen sensor based on Pd/TiO2 composite film

Hydrogen sensors with fast response and recovery rate based on nanoporous palladium (Pd) and titanium dioxide (TiO₂) composite films supported by anodic aluminum oxide (AAO) template have been demonstrated. Nanoporous TiO₂ film was sprayed on the porous AAO templates, followed by Pd film deposited on TiO₂ layer by DC magnetron sputtering. We have researched the detection performance of the hydrogen sensors depending on different thickness of TiO₂ layer from 6 to 30 nm with keeping the thickness of Pd as 30 nm. The results have demonstrated the sensors with 10 nm thickness of TiO₂ achieve the best performance with a response/recovery time as short as 4/8s at 0.8% and 0.4% hydrogen concentration, respectively. The sensors exhibited very good performance under hydrogen concentrations from 0.4% to 1.8%.     

Tailoring electrochemical efficiency of hydrogen evolution by fine tuning of TiOx/RuOx composite cathode architecture

Here we report an approach to design composite cathode based on TiO_x nanotubes decorated with RuO_x nanowhiskers for efficient hydrogen evolution. We tailor catalytic activity of the cathodes by adjustment of morphology of TiO_x nanotubular support layer along with variation of RuO_x loaded mass and assess its performance using electrochemical methods and wavelet analysis.The highest energy efficiency of hydrogen evolution is observed in 1 M H₂SO₄ electrolyte to be ca. 64% at −10 mA/cm² for cathodes of the most developed area, i.e. smaller diameter of tubes, with enhanced RuO_x loading. The efficiency is favored by detachment of small hydrogen bubbles what is revealed by wavelet analysis and is expressed in pure noise at wavelet spectrum. At increased current density, −50 or −100 mA/cm², better efficiency of composite cathodes is supported by titania nanotubes of larger diameter due to an easier release of large hydrogen bubbles manifested in less periodic events appeared in the frequency region of 5–12 s at the spectra.We have shown that efficiency of the catalysts is determined by a pre-dominant type of hydrogen bubble release at different operation regimes depending on specific surface and a loaded mass of ruthenia.     

Hydrogen permeation from F82H wall of ceramic breeder pebble bed: The effect of surface corrosion

Understanding the permeation behavior of tritium from a pebble bed breeding blanket is essential for establishing a self-sufficient fuel cycle in a nuclear fusion reactor. It is known that double corrosion layers forms on reduced activation ferritic-martensitic (RAFM) steel surface by gas release from a ceramic breeder material, however, its effect on hydrogen permeation behavior has not been elucidated. Herein, in-situ measurement of hydrogen permeation through an F82H RAFM wall of a ceramic breeder pebble bed was performed under H₂-added sweep gas conditions. The corrosion layer formed on the F82H sample had a dense microstructure, which reduced hydrogen permeation flux at least by one order of magnitude. The permeation reduction factors were 20–50 at the water-coolant temperature of a blanket. A self-repairing ability is expected for the surface oxide layer as the corrosion occurs spontaneously inside a breeding blanket.     

Effect of rGO on Fe2O3–TiO2 composite incorporated NiP coating for boosting hydrogen evolution reaction in alkaline solution

Fe₂O₃–TiO₂ composite incorporated NiP coating is a known promising catalytic coating for electrocatalytic Hydrogen Evolution Reaction (HER). It is explored in the present study that the activity of the coating can be enhanced by incorporation of rGO. The Fe₂O₃–TiO₂/rGO, electrocatalyst is synthesized by a facile hydrothermal method. Various compositions of the Fe₂O₃–TiO₂/rGO incorporated NiP coatings on mild steel substrate are developed by a chemical reduction method. The developed Fe₂O₃–TiO₂/rGO composite coating exhibits effective hydrogen evolution reaction activity with a Tafel slope of 98 mV dec⁻¹ and a low overpotential of 96 mV at a current density of 10 mA cm⁻². The hydrogen evolution reaction mechanism comprises of Volmer (adsorption of Hydrogen atom) followed by Heyrovskii (reduction to H₂). The enhanced catalytic activity by the incorporation of rGO into the coating is due to three dimensional projections of nano Fe₂O₃–TiO₂ on the folded surface of rGO. It effectively enhances the electrochemically active surface area of the coated electrode. The electrode is highly stable during alkaline HER. These results reveal that Fe₂O₃–TiO₂/rGO can be treated as an effective electrocatalyst during HER from alkaline solutions. The conclusions pave the way for exploration of new similar catalysts for other applications.     

Influence of microstructure on the hydrogen permeation of alumina coatings

In this work, the influence of microstructure on the hydrogen permeation property of alumina coatings was investigated. The different microstructures were obtained by annealing coatings at 700 °C or 900 °C. The permeation measurements showed that the 700 °C annealed coating exhibited lower hydrogen permeability than the 900 °C annealed coating. The 700 °C annealed coating was amorphous alumina. While, the 900 °C annealed coating had the spinel MnCr₂O₄ phase and γ-alumina. This spinel MnCr₂O₄ formed a network on the coating surface compared with the fine and smooth surface of the 700 °C annealed coating. The MnCr₂O₄ network in the 900 °C annealed coating formed short-cut for hydrogen diffusion, and thus resulted in high permeability. Furthermore, apparent delamination of coating was illustrated on the 900 °C annealed coating after the permeation test, and this was another reason for the high permeability of coating.     

Photodeposition of amorphous MoSx cocatalyst on TiO2 nanosheets with {001} facets exposed for highly efficient photocatalytic hydrogen evolution

Semiconductor-based photocatalytic hydrogen production is a promising approach to convert solar energy to renewable and clean hydrogen energy. However, development of cheap and efficient hydrogen evolution cocatalyst to replace noble metal based cocatalysts remains a challenge. Here, we report a MoS_x/TiO₂ nanohybrid prepared by a facile photo-assisted deposition method. The amorphous MoS_x grows intimately on the single-crystalline TiO₂ nanosheet with {001} facets exposed to form a heterojunction, which can not only facilitate the charge separation and transfer, but also provide plenty of active sites for hydrogen evolution reaction owing to abundant unsaturated S atoms on amorphous MoS_x. As a result, the MoS_x/TiO₂ nanohybrid shows a remarkable enhancement in photocatalytic hydrogen evolution performance in comparison to bare TiO₂ nanosheet. The best 0.5%-MoS_x/TiO₂ nanohybrid exhibits a hydrogen production rate at 1835.7 μmol g^?1 h^?1 under Xenon light irradiation, which is about 177 times higher than that of bare TiO₂ nanosheet. This work paves a way for the design and construction of low-cost and noble-metal-free photocatalysts for efficient photocatalytic hydrogen evolution.     

Spontaneous dissociation of H2 and high energy barrier of H invasion on W doped Al2O3(0001) surface

In view of the wide use of tungsten in fusion experimental devices and the importance of hydrogen isotopes permeation, here we studied the adsorption, dissociation, diffusion and invasion behavior of hydrogen on W doped α-Al₂O₃ (0001) surface. Based on the first-principle approaches, we found the W substitution for a top surface Al atom is the most energetically favorable. H₂ molecule prefers to be adsorbed on the surface W and spontaneously dissociates into two H anions. Near the W defects, H atoms favor to be adsorbed at the W and Al sites rather than O sites on the surface, and within the subsurface layer H can only bond to W stably. As a result, H migration to subsurface should occur around W with an energy barrier as large as 4.22 eV which is much larger than the 1.91 eV around the O atom on undoped α-Al₂O₃ (0001) surface. These findings suggest that W surface doping is beneficial to α-Al₂O₃ as tritium permeation barrier.     

Magnetic CoOx@C-Reduced graphene oxide composite with catalytic activity towards hydrogen generation

Cobalt-containing magnetic core-shell structures are alternative catalysts with better catalytic performance for hydrogen evolution. In this study, a facile route is adopted to fabricate a CoO_x@carbon-reduced graphene oxide composite containing Co nanoparticle cores, carbon shells, and reduced graphene oxide. During hydrogen generation through the catalytic hydrolysis of NaBH₄ and NH₃BH₃, the surface of CoO_x cores provides active catalytic sites, and the carbon shells protect the CoO_x cores from aggregating into gigantic cobalt oxide granules. The magnetism of CoO_x anchored onto reduced graphene oxide sheets achieves effectively a momentum transfer assisted by a motional external magnetic field. In a batch reactor, the composite exhibits a higher catalytic activity in a self-stirring mode than that in a magneton-stirring mode. This simple and efficient synthesis strategy is highly promising for the next development of both facile hydrogen generation and core-shell composite functional materials.     

Influence of silicon on hot-dip aluminizing process and subsequent oxidation for preparing hydrogen/tritium permeation barrier

The development of the International Thermonuclear Experimental Reactor (ITER) requires the production of a material capable of acting as a hydrogen/tritium permeation barrier on low activation steel. It is well known that thin alumina layer can reduce the hydrogen permeation rate by several orders of magnitude. A technology is introduced here to form a ductile Fe/Al intermetallic layer on the steel with an alumina over-layer. This technology, consisting of two main steps, hot-dip aluminizing (HDA) and subsequent oxidation behavior, seems to be a promising coating method to fulfill the required goals. According to the experiments that have been done in pure Al, the coatings were inhomogeneous and too thick. Additionally, a large number of cracks and porous band could be observed. In order to solve these problems, the element silicon was added to the aluminum melt with a nominal composition. The influence of silicon on the aluminizing and following oxidation process was investigated. With the addition of silicon into the aluminum melt, the coating became thinner and more homogeneous. The effort of the silicon on the oxidation behavior was observed as well concerning the suppression of porous band and cracks.     

Metal-organic framework derived Ni/Mo2C/Mo2TiC2Tx@NC as an efficient electrocatalyst for enhanced hydrogen production

Metal-organic framework's (MOF) shortcomings, such as poor conductivity, poor stability, and easy aggregation, impede its development in various application fields. Ni/Mo₂C/Mo₂TiC₂T_x@NC, a high-performance electrocatalyst for hydrogen evolution reaction, was prepared by incorporating a Mo₂TiC₂T_x MXene conductive matrix into MOF (namely C–Y). The Ni/Mo₂C/Mo₂TiC₂T_x@NC electrocatalyst demonstrates a remarkable HER ability with an overpotential of 105 and 134 mV and Tafel slope of 58 and 75 mV dec⁻¹ at a current density of 10 mA cm⁻² in 0.5 M H₂SO₄ and 1.0 M KOH, respectively. The outperformed HER activity of Ni/Mo₂C/Mo₂TiC₂T_x@NC catalyst is ascribe to the introduction of conductive Mo₂TiC₂T_x MXene as a carrier to improve the poor conductivity of MOF, the synergistic effect of Ni and Mo₂C nanoparticles, and the protective effect of the carbon layer. The work not only provides an experimental approach to address the problem of poor conductivity of MOF, but also provides a high-performance electrocatalyst for HER reactions. By utilizing MOFs and MXene as the precursor and the conducting carrier, our work provides some experimental reference for fabrication of multi-component inexpensive electrocatalysts.     

Improved hydrogen permeation through thin Pd/Al2O3 composite membranes with graphene oxide as intermediate layer

Here we proposed the decreasing in the roughness of asymmetric alumina (Al₂O₃) hollow fibers by the deposition of a thin graphene oxide (GO) layer. GO coated substrates were then used for palladium (Pd) depositions and the composite membranes were evaluated for hydrogen permeation and hydrogen/nitrogen selectivity. Dip coating of alumina substrates for 45, 75 and 120 s under vacuum reduced the surface mean roughness from 112.6 to 94.0, 87.1 and 62.9 nm, respectively. However, the thicker GO layer (deposited for 120 s) caused membrane peel off from the substrate after Pd deposition. A single Pd layer was properly deposited on the GO coated substrates for 45 s with superior hydrogen permeance of 24 × 10⁻⁷ mol s⁻¹m⁻² Pa⁻¹ at 450 °C and infinite hydrogen/nitrogen selectivity. Activation energy for hydrogen permeation through the Al₂O₃/GO/Pd composite membrane was of 43 kJ mol⁻¹, evidencing predominance of surface rate-limiting mechanisms in hydrogen transport through the submicron-thick Pd membrane.